[go: up one dir, main page]

WO2020086835A1 - Couche barrière de protection pour batteries alcalines - Google Patents

Couche barrière de protection pour batteries alcalines Download PDF

Info

Publication number
WO2020086835A1
WO2020086835A1 PCT/US2019/057844 US2019057844W WO2020086835A1 WO 2020086835 A1 WO2020086835 A1 WO 2020086835A1 US 2019057844 W US2019057844 W US 2019057844W WO 2020086835 A1 WO2020086835 A1 WO 2020086835A1
Authority
WO
WIPO (PCT)
Prior art keywords
anode
barrier layer
cathode
battery
electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2019/057844
Other languages
English (en)
Inventor
Jinchao Huang
Sanjoy Banerjee
Alexander Couzis
Andrew Naukam
Michael NYCE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Urban Electric Power Inc
Original Assignee
Urban Electric Power Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Urban Electric Power Inc filed Critical Urban Electric Power Inc
Priority to US17/287,928 priority Critical patent/US20210399305A1/en
Publication of WO2020086835A1 publication Critical patent/WO2020086835A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/70—Arrangements for stirring or circulating the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H01M10/286—Cells or batteries with wound or folded electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/32—Nickel oxide or hydroxide electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This disclosure relates to batteries including electrochemical cells.
  • Alkaline cells have been predominantly used as primary batteries.
  • the one-time use of primary batteries results in large material wastage as well as undesirable environmental consequences.
  • potential economic losses can arise due to the significant imbalance between the energy that is required to manufacture these cells compared to the energy that can be actually stored. As a consequence, there is a clear advantage to provide rechargeable or secondary cells.
  • an alkaline battery comprises an anode, a cathode, a separator disposed between the anode and the cathode, a barrier layer disposed between the anode and the cathode, and an electrolyte in fluid communication with the anode, the cathode, and the separator.
  • the barrier layer is at least one of: an organic polymer film or a porous inorganic layer or combinations thereof.
  • an anode comprises an electrode material comprising zinc, and a barrier layer disposed on the electrode material.
  • the barrier layer is at least one of: an organic polymer film or a porous inorganic layer or combinations thereof.
  • a method of forming a battery comprises providing an electroactive material, disposing a barrier layer on the electroactive material, and disposing the electroactive material with the barrier layer in a housing to form the battery.
  • the barrier layer is at least one of: an organic polymer film or a porous inorganic layer or combinations thereof.
  • Figure 1 schematically illustrates a battery according to an embodiment.
  • Figure 2 schematically illustrates an electrode according to an embodiment.
  • FIG. 3 schematically illustrates another battery according to another embodiment.
  • Figure 4 illustrates an electrode having a barrier layer disposed thereon according to an embodiment.
  • the terms“negative electrode” and“anode” are both used to mean“negative electrode.”
  • the terms“positive electrode” and“cathode” are both used to mean“positive electrode.”
  • Reference to an“electrode” alone can refer to the anode, cathode, or both.
  • Reference to the term“primary battery” e.g.,“primary battery,”“primary electrochemical cell,” or“primary cell”
  • Reference to the term“secondary battery” e.g., “secondary battery,”“secondary electrochemical cell,” or“secondary cell”
  • a barrier layer which is inexpensive, inert and stable in the electrolyte, highly hydrophilic for easy electrolyte accessibility, and mechanically strong to prevent electrical short circuits.
  • the present devices and methods relate to methods for making protective barrier layers in a battery, methods for laminating such barrier layer with electrodes, and methods for laminating such barrier layer with other separator films. Alkaline batteries containing such barriers and electrodes are also described.
  • barrier layer e.g., films, coatings, etc.
  • This barrier layer can be inert and stable in the electrolyte for long-term use.
  • the barrier layer can be highly hydrophilic, and enable an electrolyte reservoir at the electrode surface, which mitigates electrode degradation by maintaining a supply of electrolyte throughout the discharge/charge cycling.
  • the barrier layer can provide enhanced tortuosity to disrupt dendritic growth and support the performance of the regular separator membranes.
  • the barrier layer can fully cover one or more of the electrodes and can be sufficiently mechanically strong to prevent the exposed current collector from cutting through the regular membrane to prevent the electrical short circuits from happening.
  • a method includes selecting an organic material for the barrier layer.
  • the materials can include, but are not limited to, polyethylene, polypropylene, polyester, polyamide, cellulose acetate, cellophane, polyvinyl chloride, and polyvinyl alcohol.
  • a method can also include selecting an inorganic material for the barrier layer.
  • the materials can include, but are not limited to, ceramic materials and/or films such as zeolites, Nasicons, Lithicons, and inorganic films made with water insoluble metal oxide, metal hydroxide, and layered double hydroxide(s).
  • a method of forming an electrode and cell can include laminating the electrode with the barrier.
  • the electrode can be the anode, the cathode, or both.
  • the laminating process can be carried out by using a heated laminator, by winding the electrode sheet with the barrier layer, and/or by coating the electrode with a dispersion containing the barrier material.
  • a method can include laminating the barrier layer with the separator films.
  • the materials of the separator films can include, but are not limited to, polyethylene, polypropylene, polyester, polyamide, cellulose acetate, cellophane, polyvinyl chloride, and polyvinyl alcohol.
  • the laminating methods include but are not limited to, using a heated laminator, by winding the barrier layer with the separators, and/or by coextrusion of the films.
  • a method for making a battery comprises a cathode, an anode, and a separator disposed between the anode and the cathode. At least one of the electrodes is laminated with a layer of the layer film.
  • a battery 10 has a housing 6, a cathode current collector 1, a cathode material 2, a separator 3, an anode current collector 4, and an anode material 5.
  • Figure 1 shows a prismatic battery arrangement.
  • the battery can be a cylindrical battery (e.g., as shown in Figure 3) having the electrodes arranged concentrically or in a rolled configuration in which the anode and cathode are layered and then rolled to form a jellyroll configuration.
  • An electrolyte can be dispersed in an open space throughout battery 10.
  • the cathode current collector 1 and cathode material 2 are collectively called either the cathode 12 or the positive electrode 12, as shown in Figure 2.
  • the anode current collector 4 and the anode material 5 are collectively called either the anode 13 or the negative electrode 13.
  • the battery 10 can comprise one or more cathodes 12 and one or more anodes 13.
  • the electrodes can be configured in a layered configuration such that the electrodes alternate (e.g., anode, cathode, anode, etc.). Any number of anodes 13 and/or cathodes 12 can be present to provide a desired capacity and/or output voltage.
  • the cathode 12 can comprise a mixture of components including an electrochemically active material, a binder, a conductive material, and one or more additional components that can serve to improve the lifespan, rechargeability, and electrochemical properties of the cathode 12.
  • the cathode 12 can be incorporated into the battery 10.
  • the cathode can comprise an active cathode material (e.g., an electroactive material).
  • Suitable materials can include, but are not limited to, manganese oxide, manganese dioxide, copper manganese oxide, hausmannite, manganese oxide, copper intercalated bismuth bimessite, bimessite, todokorite, ramsdellite, pyrolusite, pyrochroite, nickel hydroxide, sintered nickel, nickel oxyhydroxide, potassium permanganate, cobalt oxide, silver oxide, silver, lithium manganese oxide, lithium manganese nickel cobalt oxide, lithium iron phosphate, copper oxide, manganese oxide, lithium vanadium phosphate, vanadium phosphate, vanadium pentoxide, nickel, copper, copper hydroxide, lead, lead hydroxide, lead oxide, or a combination thereof.
  • the cathode can be an air electrode and/or carbon electrode.
  • the active cathode material can based on one or many polymorphs of Mn0 2 . including electrolytic (EMD), a-MnC b-Mh0 2 , g-Mh0 2 . d-Mh0 2 , e- Mn0 2 , or l-Mh0 2 .
  • EMD electrolytic
  • a-MnC b-Mh0 2 g-Mh0 2
  • g-Mh0 2 g-Mh0 2
  • d-Mh0 2 e- Mn0 2
  • l-Mh0 2 l-Mh0
  • Mn0 2 can also be present such as pyrolusite, ramsdellite, nsutite, manganese oxyhydroxide (MnOOH), a-MhOOH, g-MhOOH, b-MhOOH, manganese hydroxide [Mn(OH) 2 ], partially or fully protonated manganese dioxide, Mh 3 0 4 , Mn 2 0 3 , bixbyite, MnO, lithiated manganese dioxide, zinc manganese dioxide.
  • the cycled form of manganese dioxide in the cathode can have a layered configuration, which in some embodiment can comprise d-Mh0 2 that is interchangeably referred to as bimessite.
  • non- bimessite polymorphic forms of manganese dioxide are used, these can be converted to bimessite in-situ by one or more conditioning cycles as described in more details below.
  • a full or partial discharge to the end of the Mn0 2 second electron stage e.g., between about 20% to about 100% of the 2 nd electron capacity of the cathode
  • a conductive additive such as conductive carbon enables high loadings of an electroactive material in the cathode material, resulting in high volumetric and gravimetric energy density.
  • the conductive carbon can be present in a concentration between about 1-30 wt%.
  • Such conductive carbon include single walled carbon nanotubes, multi- walled carbon nanotubes, graphene, carbon blacks of various surface areas, and others that have specifically very high surface area and conductivity. Higher loadings of the electroactive material in the cathode are, in some embodiments, desirable to increase the energy density.
  • conductive carbon examples include TIMREX Primary Synthetic Graphite (all types), TIMREX Natural Flake Graphite (all types), TIMREX MB, MK, MX, KC, B, LB Grades(examples, KS15, KS44, KC44, MB15, MB25, MK15, MK25, MK44, MX15, MX25, BNB90, LB family) TIMREX Dispersions; ENASCO 150G, 210G, 250G, 260G, 350G, 150P, 250P; SUPER P , SUPER P Li, carbon black (examples include Ketjenblack EC-300J, Ketjenblack EC-600JD, Ketjenblack EC-600JD powder), acetylene black, carbon nanotubes (single or multi-walled), carbon nanotubes plated with metal like nickel and/or copper, graphene, graphyne, graphene oxide, Zenyatta graphite
  • the bimessite discharge reaction comprises a dissolution-precipitation reaction where Mn 3+ ions become soluble and precipitate out on the conductive carbon as Mn 2+ .
  • This second electron process involves the formation of a non-conductive manganese hydroxide [Mn(OH) 2 ] layer on the conductive graphite.
  • the conductive additive can have a particle size range from about 1 to about 50 microns, or between about 2 and about 30 microns, or between about 5 and about 15 microns.
  • the conductive additive can include expanded graphite having a particle size range from about 10 to about 50 microns, or from about 20 to about 30 microns.
  • the mass ratio of graphite to the conductive additive can range from about 5: 1 to about 50: 1, or from about 7: 1 to about 28: 1.
  • the total carbon mass percentage in the cathode paste can range from about 5% to about 30% or between about 10% to about 20%.
  • the addition of a conductive component such as metal additives to the cathode material may be accomplished by addition of one or more metal powders such as nickel powder to the cathode mixture.
  • the conductive metal component can be present in a concentration of between about 0-30 wt%.
  • the conductive metal component may be, for example, nickel, copper, silver, gold, tin, cobalt, antimony, brass, bronze, aluminum, calcium, iron or platinum.
  • the conductive metal component is a powder.
  • a second conductive metal component is added to act as a supportive conductive backbone for the first and second electron reactions to take place.
  • the second electron reaction has a dissolution-precipitation reaction where Mn 3+ ions become soluble in the electrolyte and precipitate out on the graphite resulting in an electrochemical reaction and the formation of manganese hydroxide [Mn(OH) 2 ] which is non-conductive.
  • Mn(OH) 2 manganese hydroxide
  • Suitable second component include transition metals like Ni, Co, Fe, Ti and metals like Ag, Au, Al, Ca. Salts of such metals are also suitable. Transition metals like Co also help in reducing the solubility of Mn 3+ ions.
  • Such conductive metal components may be incorporated into the electrode by chemical means or by physical means (e.g. ball milling, mortar/pestle, spex mixture).
  • an example of such an electrode comprises 5-95% bimessite, 5-95% conductive carbon, 0-50% second conductive metal component and 1-10% binder.
  • a binder can be used in the cathode material.
  • the binder can be present in a concentration of between about 0-10 wt% of the cathode material.
  • the binder comprises water-soluble cellulose-based hydrogels, which were used as thickeners and strong binders, and have been cross-linked with good mechanical strength and with conductive polymers.
  • the binder may also be a cellulose film sold as cellophane.
  • the binders were made by physically cross-linking the water-soluble cellulose- based hydrogels with a polymer through repeated cooling and thawing cycles.
  • CMC carboxy methyl cellulose
  • PVA polyvinyl alcohol
  • the binder compared to the traditionally-used TEFLON®, shows superior performance.
  • TEFLON® is a very resistive material, but its use in the industry has been widespread due to its good rollable properties. This, however, does not rule out using TEFLON® as a binder. Mixtures of TEFLON® with the aqueous binder and some conductive carbon were used to create rollable binders.
  • the binder is water-based, has superior water retention capabilities, adhesion properties, and helps to maintain the conductivity relative to an identical cathode using a TEFLON® binder instead.
  • hydrogels include methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroypropyl cellulose (HPH), hydroypropylmethyl cellulose (HPMC), hydroxethylmethyl cellulose (HEMC), carboxymethylhydroxyethyl cellulose and hydroxyethyl cellulose (HEC).
  • crosslinking polymers examples include polyvinyl alcohol, polyvinylacetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride and polypyrrole.
  • a 0-10 wt% solution of water-cased cellulose hydrogen is cross linked with a 0-10% wt solution of crosslinking polymers by, for example, repeated freeze/thaw cycles, radiation treatment or chemical agents (e.g. epichlorohydrin).
  • the aqueous binder may be mixed with 0-5% TEFLON® to improve manufacturability.
  • Additional elements can be included in the cathode material including a bismuth compound and/or copper/copper compounds, which together allow improved galvanostatic battery cycling of the cathode.
  • the copper and/or bismuth can be incorporated into the layered nanostructure of the bimessite.
  • the resulting bimessite cathode material can exhibit improved cycling and long term performance with the copper and bismuth incorporated into the crystal and nanostructure of the bimessite.
  • the cathodes 12 can be produced using methods implementable in large-scale manufacturing.
  • the cathode 12 can be capable of delivering the full second electron capacity of 617 mAh/g of the Mn0 2 .
  • Excellent rechargeable performance can be achieved for both low and high loadings of Mn0 2 in the mixed material, allowing the cell/battery to achieve very high practical energy densities.
  • the cathode material 2 can be formed on a cathode current collector 1 formed from a conductive material that serves as an electrical connection between the cathode material and an external electrical connection or connections.
  • the cathode current collector 1 can be, for example, nickel, steel (e.g., stainless steel, etc.), nickel-coated steel, nickel plated copper, tin-coated steel, copper plated nickel, silver coated copper, copper, magnesium, aluminum, tin, iron, platinum, silver, gold, titanium, half nickel and half copper, or any combination thereof.
  • the cathode current collector may be formed into a mesh (e.g., an expanded mesh, woven mesh, etc.), perforated metal, foam, foil, perforated foil, wire screen, a wrapped assembly, or any combination thereof.
  • the current collector can be formed into or form a part of a pocket assembly.
  • a tab e.g., a portion of the cathode current collector 1 extending outside of the cathode material 2 as shown at the top of the cathode 12 in Figure 1A
  • a tab can be coupled to the current collector to provide an electrical connection between an external source and the current collector.
  • the cathode material 2 can be adhered to the cathode current collector 1 by pressing at, for example, a pressure between 1,000 psi and 20,000 psi (between 6.9* 10 6 and 1.4* 10 8 Pascals).
  • the cathode material 2 may be adhered to the cathode current collector 1 as a paste in some embodiments and/or as a film of cathode material.
  • the battery 10 can also comprise an anode 13 having an anode material 5 in electrical contact with an anode current collector 4.
  • the anode material e.g., the electroactive component
  • the anode material 5 can comprise zinc, which can be present as elemental zinc and/or zine oxide.
  • the zinc anode can be in the form of a Zn metal foil, a Zn mesh, a perforated Zn metal foil.
  • the Zn anode mixture comprises Zn, zinc oxide (ZnO), an electronically conductive material, and a binder.
  • the Zn may be present in the anode material 5 in an amount of from about 50 wt.% to about 90 wt.%, alternatively from about 60 wt.% to about 80 wt.%, or alternatively from about 65 wt.% to about 75 wt.%, based on the total weight of the anode material. In an embodiment, Zn may be present in an amount of about 85 wt.%, based on the total weight of the anode material. Additional elements that can be in the anode in addition to the zinc or in place of the zinc include, but are not limited to, lithium, aluminum, magnesium, iron, cadmium and a combination thereof.
  • ZnO may be present in an amount of from about 5 wt.% to about 20 wt.%, alternatively from about 5 wt.% to about 15 wt.%, or alternatively from about 5 wt.% to about 10 wt.%, based on the total weight of anode material. In an embodiment, ZnO may be present in anode material in an amount of about 10 wt.%, based on the total weight of the anode material.
  • the purpose of the ZnO in the anode mixture is to provide a source of Zn during the recharging steps, and the zinc present can be converted between zinc and zinc oxide during charging and discharging phases.
  • an electrically conductive material may be present in the anode material in an amount of from about 5 wt.% to about 20 wt.%, alternatively from about 5 wt.% to about 15 wt.%, or alternatively from about 5 wt.% to about 10 wt.%, based on the total weight of the anode material. In an embodiment, the electrically conductive material may be present in anode material in an amount of about 10 wt.%, based on the total weight of the anode material.
  • the electrically conductive material is used in the Zn anode mixture as a conducting agent, e.g., to enhance the overall electric conductivity of the Zn anode mixture.
  • electrically conductive material suitable for use in this disclosure include any of the conductive carbons described herein such as carbon, graphite, graphite powder, graphite powder flakes, graphite powder spheroids, carbon black, activated carbon, conductive carbon, amorphous carbon, glassy carbon, and the like, or combinations thereof.
  • the conductive material can also comprise any of the conductive carbon materials described with respect to the cathode material including, but not limited to, acetylene black, single walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphyne, or any combinations thereof
  • the anode material may also comprise a binder.
  • a binder functions to hold the electroactive material particles (e.g., Zn used in anode, etc.) together and in contact with the current collector.
  • the binder is present in a concentration of 0-10 wt%.
  • the binders may comprise water-soluble cellulose-based hydrogels like methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroypropyl cellulose (HPH), hydroypropylmethyl cellulose (HPMC), hydroxethylmethyl cellulose (HEMC), carboxymethylhydroxyethyl cellulose and hydroxyethyl cellulose (HEC), which were used as thickeners and strong binders, and have been cross-linked with good mechanical strength and with conductive polymers like polyvinyl alcohol, polyvinylacetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride and polypyrrole.
  • the binder may also be a cellulose film sold as cellophane.
  • the binder may also be TEFLON®, which is a very resistive material, but its use in the industry has been widespread due to its good rollable properties.
  • the binder may be present in anode material in an amount of from about 2 wt.% to about 10 wt.%, alternatively from about 2 wt.% to about 7 wt.%, or alternatively from about 4 wt.% to about 6 wt.%, based on the total weight of the anode material. In an embodiment, the binder may be present in anode material in an amount of about 5 wt.%, based on the total weight of the anode material.
  • a current collector 4 can be used with an anode 13, including any of those described with respect to the cathode 12.
  • the anode material 5 can be pressed onto the anode current collector 4 to form the anode 13.
  • the anode and/or the cathode materials can be adhered to a corresponding current collector by pressing at, for example, a pressure between 1,000 psi and 20,000 psi (between 6.9* 10 6 and 1.4* 10 8 Pascals).
  • the cathode and anode materials may be adhered to the current collector as a paste.
  • a tab of each current collector, when present, can extend outside of the device to form the current collector tab.
  • the anode material 5 can be adhered to the anode current collector 4 by pressing at, for example, a pressure between 1,000 psi and 20,000 psi (between 6.9x l0 6 and 1.4 c 10 8 Pascals).
  • the anode material 5 may be adhered to the anode current collector 4 as a paste in some embodiments and/or as a film of cathode material.
  • a separator can be disposed between the anode 13 and the cathode 12 when the electrodes are constructed into the battery.
  • the separator 3 may comprise one or more layers. Suitable layers can include, but are not limited to, a polymeric separator layer such as a sintered polymer film membrane, polyolefin membrane, a polyolefin nonwoven membrane, a cellulose membrane, a battery-grade cellophane, a hydrophilically modified polyolefin membrane, and the like, or combinations thereof.
  • the phrase“hydrophilically modified” refers to a material whose contact angle with water is less than 45°. In another embodiment, the contact angle with water is less than 30°.
  • the contact angle with water is less than 20°.
  • the polyolefin may be modified by, for example, the addition of TRITON X-100TM or oxygen plasma treatment.
  • the separator 3 can comprise a CELGARD® brand microporous separator.
  • the separator 3 can comprise a FS 2192 SG membrane, which is a polyolefin nonwoven membrane commercially available from Freudenberg, Germany.
  • the separator can comprise a lithium super ionic conductor (LISICON®), sodium super ionic conductions (NASICON), NAFION®, a bipolar membrane, water electrolysis membrane, a composite of polyvinyl alcohol and graphene oxide, polyvinyl alcohol, crosslinked polyvinyl alcohol, or a combination thereof.
  • the separator membranes may be membranes fabricated from nylon, polyester, polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), poly( vinyl chloride) (PVC), polyvinyl alcohol, cellulose or combinations thereof.
  • an electrolyte can be present between the anode and the cathode.
  • the electrolyte can comprise an alkaline electrolyte (e.g. an alkaline hydroxide, such as NaOH, KOH, LiOH, ammonium hydroxide, or mixtures thereof).
  • the electrolyte can comprise an acidic solution, alkaline solution, ionic liquid, organic-based, solid-phase, gelled, etc. or combinations thereof that conducts proton, hydroxide, lithium, magnesium, aluminum and zinc ions.
  • Examples include chlorides, sulfates, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, perchlorates like lithium perchlorate, magnesium perchlorate, aluminum perchlorate, lithium hexafluorophosphate, [M + ][AlCl 4 ](M + )] -sulphonyl chloride or phosphoryl chloride cations, l-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl)imide, l-ethyl-3- methylimidazolium trifluoromethanesulfonate, 1 -butly- 1 -methylpyrrolidinium bis(trifluoromethylsulfonyl)imide,l -hexyl-3 -methylimidazolium hexofluorophosphate,l- ethyl-3-methylimidazolium dicyanamide,l l-methyl-3-octylim
  • the electrolyte can comprise manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), manganese triflate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium sulfate, sodium hydroxide, sodium hydroxide with dissolved zincate ions, potassium hydroxide, potassium hydroxide with dissolved zincate ions potassium permanganate, titanium sulfate, titanium chloride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium permanganate, lithium nitrate, lithium nitrite, lithium hydroxide, lithium hydroxide with dissolved
  • the battery 10 can comprise at least one layer of the protective barrier layer 100.
  • the barrier layer 100 can be electrically insulating and chemically resistant to the battery environment.
  • the barrier layer 100 can be resistant to degradation in the electrolyte used in the battery 10.
  • the barrier layer 100 can be designed with highly open structures to allow rapid transport of ions for a minimal electrolyte resistance.
  • the barrier layer can also be designed to be selectively impermeable to chemical components such as zincate ions to mitigate the formation of dendrites, which can lead to shorting of the cells.
  • the barrier layer 100 can be mechanically strong to prevent any electrical short circuits caused by exposed current collectors that can cut or pierce the barrier layer and any separators.
  • the barrier layer 100 can comprise organic and/or inorganic materials.
  • the barrier layer can comprise an organic polymer film and/or a porous inorganic layer.
  • Suitable organic materials include, but are not limited to, polyethylene, polypropylene, polyester, polyamide, cellulose acetate, cellophane, polyvinyl chloride, polyvinyl alcohol, or any combination thereof.
  • Suitable inorganic materials can include, but are not limited to, ceramic films such as zeolites, Nasicons (e.g., sodium superionic conductors), Lithicons (lithium superionic conductors), and combinations thereof, and/or inorganic layers containing water insoluble metal oxides, metal hydroxide, layered double hydroxides, and combinations thereof.
  • the organic materials and the inorganic materials can each be used individually, or in some embodiments, the materials can be layered and/or mixed to form one or layers having both organic and inorganic materials in the barrier layer.
  • the barrier layer can have a thickness ranging from about 0.5 pm to about 5 mm, or between about 1 pm to about 1 mm.
  • the poly(vinyl alcohol) (PVA) film is used as a polymer barrier layer.
  • PVA is highly hydrophilic and a good film-forming polymer.
  • PVA consists of a polymer matrix that swells with water and alkaline electrolytes, and thus provides a high ionic conductivity and easy electrolyte accessibility to the electrode.
  • a PVA film can be cold water soluble, hot water soluble, or cross-linked water insoluble.
  • the PVA molecule in the PVA used in the barrier layer can vary from a molecular weight as low as 5,000 g/mol to as high as 500,000 g/mol, and its degree of hydrolysis can vary from about 70% to about 99+%.
  • each battery 10 or cell can contain at least one layer of a separator membrane that can be used to block any dendrites forming on the anode.
  • a plurality of layers of cellophane e.g., 1-10 layers, 1-5 layers, etc.
  • the barrier layer as a separator package to provide protection to the anode, the cathode, or both.
  • a plurality of layers e.g., 1-10 layers, 1-5 layers, etc.
  • cold water soluble PVA film or hot water soluble PVA film are used together as the separator combination.
  • the barrier layer 100 can be incorporated into the battery in a number of ways.
  • the barrier layer 100 may be produced as a separate layer (e.g., a freestanding film, etc.) and added to the battery as a film during construction of the battery 10.
  • the barrier layer 100 may be laminated with the electrodes by using a heated laminator or by winding the electrode sheet together with the barrier layer, which can be in the form of a film and/or coating.
  • the barrier layer can be laminated with the anode, the cathode, or both.
  • FIG 4 illustrates an embodiment of a barrier layer 100 disposed on each side of an anode 13.
  • a layer of the barrier layer 100 can be laminated onto each side of the anode surface with a heated laminator.
  • the high temperature is usually used to soften the barrier layer film and to achieve a better lamination to the electrode surface.
  • the temperature used for lamination may vary from 20 °C to 100 °C.
  • the whole electrode sheet can be fully covered by the barrier layer 100, leaving extra length of film on the leading and trailing edges, and on the top and bottom of the electrode 13.
  • the edges of the barrier layer 100 maybe heat sealed or folded around the edges of the electrode, or just left open. While shown as being layered on the anode 13, the barrier layer 100 can also or alternatively be layered on the cathode 12 in the same manner as the anode 13.
  • the barrier layer 100 may be laminated with one or more separator membranes as well.
  • the separator membranes can include any of those described herein.
  • the laminating methods include but are not limited to by using a heated laminator, by winding the barrier layer with the separators, or by coextrusion of the films.
  • the temperature used for lamination may also vary from 20 °C to 100 °C to soften the films but not to melt them.
  • the barrier layer can be disposed on or in contact with the surface of the electrode (e.g., in direct contact with the electrode surface)
  • the barrier layer 100 may be added to or disposed on one or more electrodes in the battery 10 as a coated layer.
  • the starting barrier material comprising the organic and/or inorganic material may be first dispersed in a solvent to form a dispersion.
  • the dispersion can then be used to coat an electrode and/or a separator membrane.
  • Any suitable solvent that can sufficiently solvate the material of the barrier layer can be used.
  • the solvent can be water or organic solvent including but not limited to ethanol, acetone, propanol, butanol, hexane and benzene.
  • the coating process maybe carried out by solution casting, spray coating, dip coating, or by using a doctor-blade film coater.
  • the coating process can result in a coating of the dispersion on one or more surfaces of an electrode and/or a separator membrane. Once disposed on the electrode and/or separator, the coating layer can be dried to remove the solvent and leave behind the barrier layer 100.
  • the resulting separator membrane can then be used to cover or wrap the electrode.
  • the separator can be disposed on the electrode so that the resulting barrier layer is in contact with the electrode surface.
  • One or more layering techniques can be used to obtain the desired barrier layer with a desired thickness.
  • the barrier layer can be applied as multiple layers. Each layer can have the same or a different composition.
  • multiple barrier layers can be used in which one layer comprises an organic material as described herein, and a second layer can comprise an inorganic material as described herein. Additional layers can further be used with or without separator membranes.
  • the battery 10 can then be used in a primary or secondary battery. When used as a secondary battery, the battery 10 can be cycled during use by being charged and discharged.
  • An alkaline Zn/MnCf cylindrical cell was fabricated.
  • One layer of cold water soluble PVA film was laminated onto each side of the anode surface with a heated laminator.
  • the anode sheet was fully covered by the PVA film, leaving about 1 inch of film on the leading and trailing edges, and 0.5 inch on the top and bottom of the anode.
  • Three layers of cellophane were applied in the separator package as well, serving as extra barriers for dendrites.
  • a jelly roll was made by winding the PVA-laminated anode sheet, the cellophane and the cathode sheet together. 25 wt% KOH solution was used as the electrolyte.
  • Table 1 compares the failure percentages of cells without PVA and cells with PVA laminated anodes. While a failure percentage as high as 20.84% was observed in the non-PVA cells, most of which were associated with damage caused by exposed current collectors, laminating the anodes with a PVA layer helps with preventing such damage, and reduces the early failure to 5.90%.
  • Addition of a PVA film is also beneficial for the cell’s long-term cycling. It provides enhanced tortuosity to disrupt dendritic growth and so support the performance of the cellophane.
  • the PVA film also enables an electrolyte reservoir at the anode surface, which reduces long-term degradation by maintaining a supply of electrolyte throughout the discharge/charge cycle.
  • Table 2 summarizes the result of cycle life tests (200 Ah full capacity) of cells with cold water soluble PVA laminated anodes. It is seen that cells cycled at 15% DOD of the I st electron capacity of Mn0 2 at room temperature are able to achieve around 345 cycles, and cells cycled at 20% DOD (40 Ah) have achieved more than 200 cycles.
  • an alkaline battery comprises: an anode; a cathode; a separator disposed between the anode and the cathode; a barrier layer; and an electrolyte in fluid communication with the anode, the cathode, and the separator.
  • a second embodiment can include the alkaline battery of the first embodiment, wherein the barrier layer can be an organic polymer film or a porous inorganic layer or combinations thereof.
  • a third embodiment can include the alkaline battery of the second embodiment, wherein the organic polymer film comprises at least one of polyethylene, polypropylene, polyester, polyamide, cellulose acetate, cellophane, polyvinyl chloride, and polyvinyl alcohol, or combinations thereof.
  • a fourth embodiment can include the alkaline battery of the second or third embodiment, wherein the inorganic layer comprises at least one of the ceramic films including but not limited to Zeolites, Nasicons and Lithicons or combinations thereof.
  • a fifth embodiment can include the alkaline battery of any one of the second to fourth embodiments, wherein the inorganic layer comprises at least one of the water- insoluble metal hydroxides, metal layered double hydroxides, metal oxides or combinations thereof.
  • a sixth embodiment can include the alkaline battery of any one of the first to fifth embodiments, wherein the barrier layer is produced individually and applied as a freestanding film in the battery.
  • a seventh embodiment can include the alkaline battery of any one of the first to sixth embodiments, wherein the barrier layer is applied by coating the anode, the cathode or the separator with a dispersion of the barrier material.
  • An eighth embodiment can include the alkaline battery of the seventh embodiment, wherein the solvent for the dispersion can be water or organic solvent including but not limited to ethanol, acetone, propanol, butanol, hexane and benzene.
  • a ninth embodiment can include the alkaline battery of the seventh or eighth embodiment, wherein the coating process is carried out by solution casting, spray coating, dip coating, or by using a doctor-blade film coater.
  • a tenth embodiment can include the alkaline battery of any one of the first to ninth embodiments, wherein at least one layer of the barrier is applied.
  • An eleventh embodiment can include the alkaline battery of any one of the first to tenth embodiments, wherein the thickness of the barrier layer varies from 1 pm to lmm.
  • a twelfth embodiment can include the alkaline battery of any one of the first to eleventh embodiments, wherein the barrier layer is configured to: cover the exposed current collector and protect the cell from electrical short circuit; provide an electrolyte reservoir for easy electrolyte accessibility; and suppress the transport of zincate ions.
  • a thirteenth embodiment can include the alkaline battery of any one of the first to twelfth embodiments, wherein at least one layer of the barrier is laminated with one or more separator membranes.
  • a fourteenth embodiment can include the alkaline battery of the thirteenth embodiment, wherein the separator membranes are films fabricated from nylon, polyester, polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), poly (vinyl chloride) (PVC), polyvinyl alcohol, cellulose or combinations thereof.
  • the separator membranes are films fabricated from nylon, polyester, polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), poly (vinyl chloride) (PVC), polyvinyl alcohol, cellulose or combinations thereof.
  • a fifteenth embodiment can include the alkaline battery of the thirteenth or fourteenth embodiment, wherein the barrier layer is laminated with the separator membranes by hot pressing, by a laminator, by coextrusion, by winding or by coating.
  • a sixteenth embodiment can include the alkaline battery of any one of the first to fifteenth embodiments, wherein the barrier layer is laminated with the anode or the cathode or both.
  • a seventeenth embodiment can include the alkaline battery of the sixteenth embodiment, where in the barrier layer is laminated with the electrodes by hot pressing, by a laminator, by winding or by coating.
  • An eighteenth embodiment can include the alkaline battery of any one of the first to seventeenth embodiments, wherein the battery can be a prismatic battery or a cylindrical battery.
  • a nineteenth embodiment can include the alkaline battery of any one of the first to eighteenth embodiments, wherein the battery can be a primary battery or a rechargeable battery.
  • a twentieth embodiment can include the alkaline battery of any one of the first to nineteenth embodiments, wherein the anode comprises a pasted porous Zn electrode, a Zn metal foil, a Zn mesh, a perforated Zn metal foil.
  • a twenty first embodiment can include the alkaline battery of any one of the first to twentieth embodiments, wherein the cathode comprises a manganese dioxide electrode, a nickel oxyhydroxide electrode, a silver oxide electrode, and an air electrode.
  • the cathode comprises a manganese dioxide electrode, a nickel oxyhydroxide electrode, a silver oxide electrode, and an air electrode.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Cell Separators (AREA)

Abstract

Une batterie alcaline comprend une anode, une cathode, un séparateur disposé entre l'anode et la cathode, une couche barrière disposée entre l'anode et la cathode, et un électrolyte en communication fluidique avec l'anode, la cathode et le séparateur. La couche barrière est un film polymère organique et/ou une couche inorganique poreuse ou des combinaisons de ceux-ci.
PCT/US2019/057844 2018-10-24 2019-10-24 Couche barrière de protection pour batteries alcalines Ceased WO2020086835A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/287,928 US20210399305A1 (en) 2018-10-24 2019-10-24 A protective barrier layer for alkaline batteries

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862750038P 2018-10-24 2018-10-24
US62/750,038 2018-10-24

Publications (1)

Publication Number Publication Date
WO2020086835A1 true WO2020086835A1 (fr) 2020-04-30

Family

ID=70330520

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2019/057844 Ceased WO2020086835A1 (fr) 2018-10-24 2019-10-24 Couche barrière de protection pour batteries alcalines

Country Status (2)

Country Link
US (1) US20210399305A1 (fr)
WO (1) WO2020086835A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023076092A1 (fr) * 2021-10-26 2023-05-04 Skyre. Inc. Cellule membranaire biopolaire pour la capture de dioxyde de carbone

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL283261B2 (en) 2018-11-22 2025-06-01 Phinergy Ltd Separators with layered double hydroxides for electrochemical cells
JP2022510339A (ja) * 2018-12-05 2022-01-26 フィナジー リミテッド 二次電池におけるデンドライト成長防止
EP4018493A1 (fr) * 2019-08-20 2022-06-29 Xerox Corporation Dispositif électrochimique biodégradable
FR3152193A1 (fr) 2023-08-17 2025-02-21 Sunergy Procédé de préparation d’un générateur électrochimique

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3970472A (en) * 1975-07-08 1976-07-20 Mcgraw-Edison Company Rechargeable battery with zinc negative and dendrite barrier
US20020182488A1 (en) * 2001-05-31 2002-12-05 Cho Chung-Kun Method for forming lithium metal anode protective layer for lithium battery and lithium battery having such protective layer
US20040197641A1 (en) * 2002-10-15 2004-10-07 Polyplus Battery Company Active metal/aqueous electrochemical cells and systems
US20050074674A1 (en) * 2003-08-08 2005-04-07 David Boone Separators for alkaline electrochemical cells
US20060240317A1 (en) * 2005-04-26 2006-10-26 Powergenix Systems, Inc. Nickel zinc battery design
US20080182157A1 (en) * 2005-08-09 2008-07-31 Polyplus Battery Company Compliant seal structures for protected active metal anodes
US20160149212A1 (en) * 2013-06-21 2016-05-26 HYDRO-QUéBEC Anode for high-energy batteries
US20170062829A1 (en) * 2015-08-31 2017-03-02 Samsung Electronics Co., Ltd. Lithium metal battery

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070224495A1 (en) * 2006-03-22 2007-09-27 Gibbons Daniel W Zinc/air cell
US10573927B2 (en) * 2013-02-01 2020-02-25 Nippon Shokubai Co., Ltd. Electrode precursor, electrode, and cell
US20180358595A1 (en) * 2015-12-14 2018-12-13 Nippon Kodoshi Corporation Separator for alkaline batteries, and alkaline battery
KR102890540B1 (ko) * 2017-02-22 2025-11-26 삼성에스디아이 주식회사 멀티탭 쇼트 억제 구조를 갖는 이차 전지
JP7308634B2 (ja) * 2019-03-22 2023-07-14 ニッポン高度紙工業株式会社 アルカリ電池用セパレータ及びアルカリ電池

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3970472A (en) * 1975-07-08 1976-07-20 Mcgraw-Edison Company Rechargeable battery with zinc negative and dendrite barrier
US20020182488A1 (en) * 2001-05-31 2002-12-05 Cho Chung-Kun Method for forming lithium metal anode protective layer for lithium battery and lithium battery having such protective layer
US20040197641A1 (en) * 2002-10-15 2004-10-07 Polyplus Battery Company Active metal/aqueous electrochemical cells and systems
US20050074674A1 (en) * 2003-08-08 2005-04-07 David Boone Separators for alkaline electrochemical cells
US20060240317A1 (en) * 2005-04-26 2006-10-26 Powergenix Systems, Inc. Nickel zinc battery design
US20080182157A1 (en) * 2005-08-09 2008-07-31 Polyplus Battery Company Compliant seal structures for protected active metal anodes
US20160149212A1 (en) * 2013-06-21 2016-05-26 HYDRO-QUéBEC Anode for high-energy batteries
US20170062829A1 (en) * 2015-08-31 2017-03-02 Samsung Electronics Co., Ltd. Lithium metal battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023076092A1 (fr) * 2021-10-26 2023-05-04 Skyre. Inc. Cellule membranaire biopolaire pour la capture de dioxyde de carbone

Also Published As

Publication number Publication date
US20210399305A1 (en) 2021-12-23

Similar Documents

Publication Publication Date Title
US11342548B2 (en) Zinc electrodes with high capacity utilizations
US20210399282A1 (en) Porous zn metal electrode for zn batteries
US11482701B2 (en) Cycling protocol for alkaline batteries
US20190044129A1 (en) Rechargeable Alkaline Manganese Dioxide-Zinc Bipolar Batteries
US11152615B2 (en) Electrode designs for high energy density, efficiency, and capacity in rechargeable alkaline batteries
US20220336864A1 (en) Aqueous electrochemical cells using polymer gel electrolytes
US20210399305A1 (en) A protective barrier layer for alkaline batteries
KR102847247B1 (ko) 알칼리 배터리에서 선택성 이온 침투를 위한 이온 선택성 막
US20200227739A1 (en) Process for making manganese dioxide and its polymorphs reversible
US20210343995A1 (en) Electrochemical plating of additives on metallic electrodes for energy dense batteries
US12476287B2 (en) Dual electrolyte approach for high voltage batteries
CN115699370A (zh) 水性高电压锌-阳极电池
US20200358092A1 (en) Method of forming charged manganese oxides from discharged active materials
US20230031554A1 (en) Dual electrolyte approach to increase energy density of aqueous metal-based batteries
WO2021211453A1 (fr) Batterie haute tension sans métal
JP2023523555A (ja) 中間層による亜鉛－二酸化マンガンバッテリの性能の向上
US20220069286A1 (en) Polymer embedded electrodes for batteries
US20220384856A1 (en) Mitigating the zincate effect in energy dense manganese dioxide electrodes
US20230030182A1 (en) Battery for achieving high cycle life and zinc utilization in secondary zinc anodes using electrocoagulants
WO2025184200A1 (fr) Batteries zinc-dioxyde de manganèse à insertion de protons denses en énergie

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19877111

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19877111

Country of ref document: EP

Kind code of ref document: A1